Novel urea derivatives



United States Patent 3,275,670 NOVEL UREA DERIVATIVES Gustav Steinbrunn, Schwegenheim, Pfalz, Adolf Fischer,

Mutterstadt, Pfalz, and Erich Flickinger, Frankweiler, Pfalz, Germany, assignors to Badische Anilin- & Soda- Fabrik Aktiengesellschaft, Ludwigshafen am Rhine, Germany No Drawing. Filed Nov. 30, 1964, Ser. No. 414,882 Claims priority, application Germany, Dec. 3, 1963,

B 74,507; July 4, 1964, B 77,541

4 Claims. (Cl. 260--453) It is known that urea derivatives, for example N-pchlorophenyl-N'-methyl-N'-isobutinylurea or N-p-chl'orophenyl-N',N'-di-methylurea, may be used for controlling weeds. There action is however unsatisfactory.

We have found that selective herbicides which contain a urea derivative having the formula:

in which R denotes methyl, methoxy or sec-but-3-ynyl, R denotes an alkyl radical having up to four carbon atoms, an alkyl radical having up to four carbon atoms and bearing a hydroxyl group as a substituent, an alkenyl radical having 3 to 4 carbon atoms and bearing two or three chlorine atoms as substituents, or the trichlorobenzyl radical, X denotes a chlorine atom or a hydrogen atom, have a good eifect against broad-leaved weeds and against grasses in beet, wheat and rice. Another advantage of the herbicides is that they can be used for post-emergence treatment. Some of the urea derivatives are syrups, others are solid products. They may be prepared from corresponding substituted N-por N-m-chloromethylphenylor -chlorophenyl-N-methyl-N-alkylor -N-alkoxyor -N-alkynylureas. The substituted N-por N-m-halomethylphenylor -halophenyl-N'-methyl-N'-alkylor -N- alkoxyor -N-alkynylureas required as initial materials may be obtained from the corresponding substituted phenylisocyanates or halophenyl-isocyanate's or their carbamyl chlorides by reaction with dialkylamines, methylalkoxyamines or methylalkynylamines. The N-chloromethylphenylor N-chloromethylhalophenyl-N-dialkylor N'-alkyl-N'-alkynylureas thus obtained may be reacted with the corresponding alkyl or halogen substituted or alkenyl substituted alkenylmercaptans or their metal salts in the presence of acid-binding substances in order to obtain the urea derivatives to be contained in the herbicides according to this invention. The substituted N-phalornethylphenyl-N-methyl-N-methoxy-ureas which are also required as initial products are obtainable from the corresponding substituted phenylisocyanates by reaction with 0,N-dimethylhydroxyl-amine or by reaction with hydroxylamine and subsequent methylation, for example with dimethyl sulfate, or by reaction of the corresponding substituted phenylcarbamyl chlorides in the presence of alkali with hydroxylamine or O',N-dimethylhydroxylamine.

3,275,670 Patented Sept. 27, 1966 Suitable por m-chloromethylphenyl isocyanates or por m-chloromethylhalophenyl isocyanates are 3-chloro-4- chloromethylphenyl isocyanate, 4-chloro-3-chloromethylphenyl isocyanate, Tchloromethylphenyl isocyanate or their phenylcarbamyl chlorides.

Suitable mercaptans for the reaction are li-hydroxyethylmercaptan, 2,3 dichloroallylmercaptan, 2,3,3 trichloroallylmercaptan, 3,3 dichloromethallylmercaptan, 2,3,6 trichlorobenzylmercaptan, 3,4-dichlorobuten 3 -yl (2 mercaptan or 2,3,4-trichlorobuten-(2)-yl-(1)-mercaptan. Alkali metal salts may be chosen as the metal salts of the mercaptans.

The reaction may however be carried out in the presence of trialkylamines. The following recipes explain the production of the urea derivatives:

18 parts (by weight) of 2,3,S-trichloroallylmercaptan is added while stirring in a nitrogen atmosphere to 5.6 parts of potassium hydroxide dissolved in 120 parts of ethyl alcohol. Then, at 40 to 50 C, 28 parts of N-3- chloro- 4 -chloromethylphenyl N-methyl N'- isobutynylurea dissolved in parts of acetonitrile is dripped in. Stirring is continued for some time at 60 to 65 C. The ethyl alcohol is then evaporated at subatmospheric pressure, the residue is dissolved in ethyl acetate and water, the layers are separated and the ethyl acetate solution is Washed with water. The solution is filtered and dried and the solvent is partly removed in vacuo. The product is then precipitated by adding petroleum ether. 35 parts of N-4-(2,3',3'-trichloroallythiomethyl)-3-chlorophenyl- N'-methyl-N-sec-but-3-ynyl is obtained as a syrup (secbut-3-ynyl being the radical butyne-(l)-yl-(3)) having a chlorine content of 32.5% (calculated value 33.3%). The product has the formula:

parts (by weight) of 2,3,3-trichloroallylmercaptan is added to 28 parts of potassium hydroxide, dissolved in 400 parts of ethyl alcohol, while passing nitrogen through. While stirring at 40 to 50 C., a solution of parts of N 3 chloro-4-chloromethylphenyl-N'-methyl-N-methoxyurea in 500 parts of alcohol is dripped in and the reaction is allowed to continue at 55 to 70 C. The bulk of the solvent is then removed at subatmospheric pressure, ethyl acetate is added and the solution is washed well in a separating funnel. 190 parts of N-4-(2',3',3',- trichloroallylthiomethyl)- 3 -chlorophenyl- N'-methyl- N- methoxyurea is obtained as a syrup. The chlorine content is 36% (calculated value 35.3%). The product has the following formula:

] OCH; Cl

3 4 Other urea derivatives are listed in the following tables:

TABLES CH; R1SCH2 NH-C ON l R1 X Analysis: Cl, R: X R1 M. pt. fpercgnt I.= oun c.= calculated.

2,3,3-trichlorobenzyl Cl C4Hi Syrup e. fl-Hydroxyethyl Ol -CH; do. i. c. 3,3-dichloromethal1yl Cl CH3 104 to 105 0. Methyl C1 CH3. Syrup {L c. 2,3,3trlchloroallyl --CHa.. 75 to 76.5" (3-. 8,3-dlchl0romethallyl OGH; {L O. 2,3-diehloroallyl OCH; f. G.

OH; X- NH-C ON R1 Rr-S-CH:

2,3,3-trichloroallyl H -C'4H5 Syrup f. c. 2,3,6-trichlorobenzyl H C4H do {1. c. 3,3-diehloromethallyl Cl O H "do" {L e. 2,3,6-trichl0robeuzyl Cl H .do i. c. 2,3,3-trlehloroallyl H OCH3 f. e. 3,3-diehl0romethallyl H OCH; f. c.

D0 H OCH;- 76 C Herbicides in accordance with this invention are pre- TABLE pared by mixing the active substances with conventional carriers. They may be used either alone or mixed with Active substance other active substances. They may also be m1Xed with fertilizers and used in granulated form as herbicides.

I II Examples of additives for the production of emulsions are salts of alkylbenzenesulfonic acids, salts of ammonium ia fi g g substance used in 1 5 1 5 compounds, or oxalkylated phenol derivatives.

The invention is further illustrated by the following Crop plants. examples relating to the use of the herbicides according nice Oto 10 50 to P 10 30. to this invention. Weeds:

Wild oat: 50 to an 50. Example 1 Slender fnxtm'l 90 so to 90.

wild1 camomile $58 to 100 30 to 108. ee mix ure o 100 0 0 10 Plants of me 3m Wheat f vulgare), 55 Annual meadow grass mm 90 to 100, wild oats (Avena fatua), slender foxtail (Alopecurus myosurozdes), annual meadow grass (P d (m Wlld 0 denotes no damage and 100 denotes total destruction. camormle (Mazrzcarza chamomllla) and a mixture of Weeds consisting of sorrel (Rumex spp.), vetoh (Vicia cracca), nettle (Urtica urens), cleavers (Galium aparine), 0

White goosefoot (Chenopvdium album) and chickweed (Stellaria media), at a growth height of 3 to 12 cm. in a greenhouse are sprayed with N-4-(2,3',3'-trichloroallyl-thiomethyl)-3-chlorophenyl-N'-methyl-N'-sec but- 3-ynylurea (I) and, for comparison therewith, with N-pchlorophenyl-N-methyl-N-sec-but-3-ynylurea (II) each at a rate equivalent to the use of 1.5 kg. of active substance per hectare, dispersed in 500 liters of Water per hectare. Afiter three weeks, it is evident that N-4- (2',3,3-trichloroallylthiomethyl)-3 chlorophenyl N'- methyl-N-sec-but-'3-ynylurea (I) has a more favorable plant compatibilty with rice (Oryza sativa) and Wheat (Triticum vulgare) than N-p-chlorophenyl-N'-methyl-N'- sec-but-3-ynylurea (II).

The experimental results are given in the following table:

A similar client is achieved with the following urea derivatives as with N-4-(2',3,3-trichloroallylthiomethyl)- 3-chlorophenyl-Namethyl-N' sec but-ynylurea:

.5 Example 2 Plants of rice (Oryza sativa), Wheat (Triticum vulgare), wild oats (Avena fatua), annual meadow grass (Poa annua), camomile (Matricaria chamomilla) and an assortment of weeds consisting of cleavers (Galium aparine), vetch (.Vicz'a cracca), chickweed (Stellaria media), nettle (Urtica urens), white goosefoot (Chenep dium album) and sorrel (Rumex spp.) are planted in plastic pots. After the plants have reached a plant height of 3 to 15 cm. they are sprayed with N-4-(2,3,3'-rtrichloroallylthiomethyl)-3-chlorophenyl-N' dimethylurea (I) and, for comparison therewith, with N-p-chlorophenyl-N-dimethylurea (II), each at a rate equivalent to the use of 1.5 kg. of active substance per hectare, dispersed in 500 liters of water per hectare. I 15 Three weeks later it is evident that N-4-(2',3',3'-trichloroallylthi'omethyl)-3-chlorophenyl-N dimethylurea (I) has a considerably more favoralble plant compatibility with rice (Oryza saliva) and Wheat (Triticum vulgare) than N-p-chlorophenyl-Ndimethylurea (II).

Arable land treated with N-4-(2',3,3-trichloroallylthi omethyl)-3-chlorophenyl-N'-dimethylurea (I) may be broken up and freshly planted after three to four weeks Without the freshly emerging crop plants being damaged beet has completely grown out again, whereas the weeds and weed grasses have completely withered.

The following substances have a similar effect:

N-4- 3 ',3 -dichloromcthallylthiomethyl) -3-chlorophenyl- N-methyl-N-methoxyurea,

N-4-( 3 ,4'-dichlorobu'ten-( 3 -yl- ('2) -thiomethyl -3-ehlorophenyl-N-methyl-N-metlroxyurea and N-4- 2,3 ,4-trichlorobuten- (2) -yl- 1 )-thiomethyl -3- chlorophenyl-N'-methyl-N'-methoxyurea.

Example 4 Wheat (T riticum vulgar-e), beet (Bela vulgaris), Wild oats (Avena fatua), slender foxtail (Alopecurus mysuroides), cocks-foo-t grass (Dactylis glomeraza), mustard (Sinapis alba) and assorted weeds consisting of vetch (Vicia cracca), chickweed (Stellar-la media), nettle (Urtica urens), white go'osefooit (Ghenopodium album), camomile (Matricaria chamomilla) and sorrel (Rumex acetosa) at an average height of to cm. in a greenhouse are sprayed at the rate of 1.5 kg. per hectare with N-4-(2,3',3'-trichl0roallylthi omethyl) 3 chlorophenyl- N'-methyl-N'-methoxyurea (I) in comparison with N-pchlorophenyl-N-methyl-N'-meth-oxyuroa (II) and N- 3,4-dichlorophenyl-N-methyl-N-meth.oxyurea (III) disby th f ff f thi om und, Thi i not th persed in 500 liters of water per hectare. The results case with N-p-chlorophenyl-N'-dimethylurea. re h wn in th following t le:

The results of the experiment may be seen from the following table:

TABLE Active substance Active substance I II I II III Amount of active substance used in kg.

perhectare 1.5 1.5 lg g g 20m 30H. 80 u go.

0to10 10o 100. ail??? o n 1 so to 90. m 90.

w 10 to 20 40, Slender foxtall 70 40 601:0 70. Weeds: Oocks-iootgrass 50 to 90110100.

Wildcats 90. 90 to 100. 40 Must d 1 00 00- Annual meadow grass 90 to 100--- so to 100. Assorted Weeds 0 0- Gamomile n. 0 100.

Assorted Weeds n 90 to 100m 90 to 100' 0 denotes no damage and 100 denotes total destruction.

0 denotes no damage and 100 denotes total destruction.

The following compounds have a similar effect to N-4- 5 (.233"3"inch?manylthwmethyll'3 chlorophenyl N It may be seen from the table that active substance I dlmethylurea' has a better herbicidal activity in part than active sub- N-4-(2',3'-dichloroallylthiomethyl)-3- chl orophenyl-N- stances II and III. Compatibilty with beet and wheat dimethylurea, is clearly best of all the active substances tested with ac- N-4-(3,3'-dichloromethylallylthiomethyl)-3-chlorophen- 50 tive substance I.

yl-N-dimethylurea, The following compounds have a similar effect: Nil-fife: itrichloroallylthiomethyl) -pl1enyl-N -d1meth- T: 3 l 13 or o mheth anylthi o m ethyl! chl OT eny1 Beet (Beta vulgarz's), cocks foot .grass (Dactylis glochlomphenyl'N methoxyurea' meraza), mustard (Sinapis alba), wild oats (Avena Example 5 fatua), slender foxtail (Alopecurus myosuroides) and as- 60 sorted weeds consisting of sorrel (Rumex acetosa), Wheat (T riticum vulgare), barley (Hordeum vulgare), ribwort plaintain (Plantago laneeolata), vetch (Vz'cia maize (Zea mays), rice (Oryza sativa'), carrots (Daucus cracca), camomile (Matricaria chamomilla), chickweed carom), beans (Phaseolus vulgaris), slender foxtail (Stellaria media), small nettle (Urtz'ca urens), White (Alopecurus myosuroides), annual meadow grass (Poa go'osefoot (Chenopodz'um album) at an average height annua), wild mustard (Sinapis arvensis), amaranth of 8 to 14 cm. in a greenhouse are sprayed at a rate of (Amaranthus retroflexus), small nettle (Urtica urens) 1.5 and 3 kg. per hectare with N-4-(2',3,3-trichloroand White goosefoot (Chenopodium album) at a growth allylthiomethyl)-3-chlorophenyl-N'-methyl-N' methoxyheight of 3 to 15 cm. in a greenhouse are sprayed at the urea dispensed with an addition of sodium lignin sulfonate rate of 1.5 kg. per hectare with N-4-(3',3'-dichloroin 600 liters per hectare of water. Three weeks later methallylthiomethyl)-3-chl-orophenyl N methyl N- it is observed that the asserted weeds, coeks-foot grass and mustard have completely withered. An effect of more than 80% is achieved with slender foxtail and wild oats. The beet is inhibited in growth by only about 10%. Fourteen days later this growth inhibition of the methoxyurea (I) N-4-(2',3-dichloromethallylthiomethyl)-3-chlorophenyl-N'-methyl-N-methoxyurea (II) and, for comparison, N-3',4-dichloropheny1-N' methyl N'- methoxy-urea (III) dispersed in 500 liters per hectare of water.

The results are to be seen 1n the following table:

TABLE Active substance (1.5 kgJha.) Plants I II III Jrop plants:

heat 15. 80. Barley to 20-.... 10 40. Maize. 10 to 2O..... 10 60. Rice Oto 10...-.. O 30to 40 Carrots 0 to 10. 10 to Beans. 0 30. to Needs:

Slender foxtail 5O 50. Annual meadow grass. 80. Mustard 100 90 to 100. 10f). Amaranth.-. to 100. 100. Small nettle... 100.-.. 100. White goosefoot 90 to 100. 90 to 100. 90 to H10.

0 denotes no damage and denotes total destruction.

Example 6 The weeds white goosefoot (Chenopodium album), small nettle (Urtica urens), gallant soldier (Galinsoga parviflora), wild mustard (Sinapis arvensis), camomile (Matricaria chamemilla), vetch (Vicia sepium), knotweed (Polygonum sp.), groundsel (Senecio vulgaris), Wild thistle (Cirsium arvense), chiclcweed (Slellaria media), dead nettle (Lamium amplexicaule), annual meadow grass (Poa annua), rye grass (Lolium perenne), slender foxtail (Alopecurus myosuroides) and Wild oats (Avena fatua) at a growth height of 3 to 8 cm. on an agricultural cultivated area are sprayed at the rate of 3 kg. per hectare of N-4-(2,3-dichloromethallylthiomethyl)-3-chlorophenyl-N' methyl N methoxyurea in 500 liters per hectare of water. One or two days later, the plants begin to wither from the tips of the leaves and after eight to fourteen days all the weeds and weed grasses have withered.

The following have similar action:

N-4- (2,3,3-trichloroa11ylthiomethyl -3- chlorophenyl-N' methyl-N-methoxyurea,

8 N4 3 ',3 '-dichloromethallylthiomethyl) -3-chlorophenyl- N'-methyl-N'-met hoxyurea and N-4- (2,3 ',4'-tnichlorobuten-(2) -yl-( l)-thiomethyl) -3- chlorophenyl-N'-methyl-N'-methoxyurea.

We claim: 1. A compound having the iormula:

R:S-CH2 CH3 NHC ON\ X B1 in where R denotes a member selected from the group consisting of methyl, methoxy and sec-but-3-ynyl, R denotes a member selected from the group consisting of an alkyl radical having up to four carbon atoms, an alkyl radical having up to four carbon atoms which bears a hydroxyl group as a substituent, an alkenyl radical having three to four carbon atoms and bearing two to three chlorine atoms as substituents, and the trichlorobenzyl radical X denotes a member selected from the group consisting of hydrogen and chlorine.

2. N-4-(2,3,3'-trichloroallylthiomethyl) 3 chlorophenyl-N'-methyl-N-sec-but-3-ynylurea.

3. N-4-(2',3',3-trichloroallylthiomethyl) 3 chlorophenyl-N'-methyl-N'-methylurea.

4. N-4-(2,3,3-trichloroallylthiomethyl) 3 chlorophenyl-N'methyl-N-methoxyurea.

References Cited by the Examiner UNITED STATES PATENTS 2,744,819 5/1956 Toorman 712.6 2,863,754 12/1958 Wain 712.6 2,960,534 11/1960 Scherer et a1 260-553 2,999,110 9/1961 Lott et al 260553 ALEX MAZEL, Primary Examiner.

JAMES O. THOMAS, JR., HENRY R. JILES,

Examiners.

JAMES H. TURNIPSEED, Assistant Examiner. 

1. A COMPOUND HAVING THE FORMULA: 